S-[nu&#39;-(chlorocarbonyl)-amino] isothiocarbamyl chlorides and their preparation



United States Patent 3,301,894 S-[N'-(CHLOROCARBONYL) AMINO]ISOTHIOCAR- BAMYL CHLORIDES AND THEIR PREPARATION Gerhard F. Ottmann, Hamden, and Haywood Hooks, In,-

West Haven, Conn., assignors to Olin Mathieson Chemical Corporation, New Haven, Conn., a corporation of Virginia No Drawing. Filed Nov. 16, 1964, Ser. No. 411,638

12 Claims. (Cl. 260-544) This invention relates to a process for preparing S-[N- (chlorocarbonyl) amino] isothiocarbamyl chlorides. More particularly it relates to the preparation of a series of compounds having the following general formula:

a R--N=CSNC=O wherein R and R are either alkyl, cycloalkyl, aryl, substituted aryl, or benzyl.

It has recently been established that S-chloro isothiocarbamyl chlorides are provided by the reaction of.

various isothiocyanates with a substantially equivalent amount of chlorine at low reaction temperatures in the presence of an inert solvent. The reactions proceed as illustrated in the following equation wherein, for example, N-phenyl S-chloro isothiocarbamyl chloride is prepared by adding chlorine to phenyl isothiocyanate:

COHENCS 012 CaHsNO A more thorough and general description of the preparation of these derivatives is disclosed in our copending US. patent applications, Serial No. 354,789, filed March 25, 1964, and Serial No. 370,051, filed May 25, 1964.

The resulting S-chloro isothiocarbamyl chlorides are somewhat sensitive to heat and moisture, but they are surprisingly stable if handled properly. It has now been found that these chlorides can be reacted with a wide variety of isocyanates to provide S-[N'-(chlorocarbonyl)- amino] isothiocarbamyl chlorides having the general Formula I. An eflicient and convenient process for the preparation of the derivatives 1) in high yield and purity is disclosed herein.

Although a great number of S-chloro isothiocarbamyl chlorides having the formula RNC(C1)SC1 may be employed as reactants in the practice of this invention, it is preferred to utilize certain of these derivatives. Thus, particularly suitable reactants are those S-chloro isothiocarbamyl chlorides wherein R is alkyl having 1-18 carbon atoms, cycloalkyl having 5-7 carbon atoms such as cyclohexyl, aryl having 6-10 carbon atoms including phenyl, tolyl and xylyl, phenyl having a lower alkoxy (1-3 carbon atoms) substituent, halogenated phenyl, nitrated phenyl, and benzyl[ The preparation of these preferred S-ohloro isothiocarbamyl chlorides and other is disclosed in the aforementioned copending US. patent applications. 7

Similarly, many isocyanates can be utilized as reactants with the S-chloro isothiocarbamy chlorides to provide derivatives having the Formula I, but certain isocyanates are particularly suitable for use in the process of this invention. Thus, isocyanates R'NCO wherein R is alkyl having 1-18 carbon atoms, cycloalkyl having 5-7 carbon atoms, aryl having 6-10 carbon atoms, halogenated phenyl, nitrated phenyl, and phenyl having a lower alkoxy (1-3 carbon atoms) substituent are preferentially utilized in the practiceof this invention.

For instance, included among the isocyanates which may be employed in the preparation of the compounds ice (I) are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, 3-hexyl, n-heptyl, 4-heptyl, n-octyl, 2- ethylhexyl, n-decyl, 4-butyloctyl, octadecyl, cyclopentyl, cyclohexyl, cycleheptyl, phenyl, o-tolyl, m-tolyl, p-tolyl, 2,6-xylyl, l-naphthyl, 2-naphthyl, 2 chlorophenyl, 3- chlorophenyl, 4-chlorophenyl, 4-bromophenyl, 3-bromotolyl, 4-fluorophenyl, 2,4-di'bromophenyl, 3,4-dichlorophenyl, 2,5-dichlorophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 3,5-dinitrophenyl, 2,4,6- trinitrophenyl, 3-methoxyphenyl, 4-methoxyphenyl, pethoxyphenyl, phenethyl, benzyl, and m-methoxybenzyl isocyanates.

The S [N' (chlorocar-bonyD-amino] isothiocarbamyl chlorides of this invention are readily prepared by reacting the isocyanates with the S-chloro isothiocarbamyl chlorides in the presence of an inert diluent. Included among the diluents which are suitable for use in the process are ether, various aromatics such as benzene and toluene, aliphatic hydrocarbons such as hexane, heptane, and chlorinated hydrocarbons as, for example, carbon tetrachloride. I

The process of this invention is carried out preferentially at a reaction temperature range of about 0 C. to about 60 C. and even more optimally at a range of about 1530 C.

The products can be isolated at the completion of the reaction period by conventional procedures such as filtration, etc. They may also be isolated by merely stripping the diluent employed from the reaction mixture to obtain, the residual product.

The following examples will serve to illustrate the preparation of several of the S[N-(chlorocarbonyl)- amino] isothiocar-bamyl chlorides (I) in accordance with this invention.

Example 1 To a solution of 24.0 g. of ethyl isocyanate in ml.

of ether was added an amount of 70.0 g. of N-phenyl S-chloro isothiocarbamyl chloride dropwise and with stirring. The slightly exothermic reaction was controlled at a temperature of between 20 and 25 C. by means of an external cooling bath of 15 C. After complete addition, the reaction mixture was stirred for 16 more hours at room temperature. During this period a white precipitate had formed which was separated by filtration, washed with dry pentane, and dried in vacuo affording 85.0 g. (91% of the theory) of N-phenyl S-[N-chlorocarbonyD-ethylamino] isothiocarbamyl chloride, M.P. 108 109 0., in the form of a white microcrystalline solid.

Analysis.Calcd. for C H Cl N OS: N. 10.10; S, 11.54. Found: N, 10.06; S, 12.01.

Example 2 A total of 75.0 g. of N-phen-yl S-chloro isothiocarbamyl chloride was added dropwise to a stirred solution of 48.0 g. of p-tolyl isocyanate in 2.00 ml. of ether. A temperature of 25 to 30 C. was maintained throughout the reaction. After standing for 16 additional hours the white precipitate which had formed during the reaction was removed by filtration, washed with dry ether and dry pentane, and dried in vacuo affording 103 g. (84% of the theory) of N-phenyl S-[N'-(chlorocarbonyl)-ptolylamino] isothiocarbamyl chloride in the form of a whitesolid, M.P. 9596 C.

Analysis.'-Calcd. for C H Cl N OS: N, 8.25; S, 9.43. Found: N, 8.04; S, 9.38. Molecular weight: Calcd. 339.3; found 337.

Example 3 lution of 40.0 g. of butyl isocyanate in 500 ml. ether within a period of 45 minutes. The reaction was exothermic, and a precipitate started to appear after approximately g. of the chloride had been added. The re- 2. The compounds of claim 1 wherein R and R are each alkyl having 1-18 carbon atoms.

3. The compounds of claim 1 wherein R and R are each aryl having 6l0 carbon atoms.

action temperature was maintained between and 5 4. The compounds of claim 1 wherein R is aryl hav- C. After complete addition, the mixture was stirred ing 6-10 carbon atoms and R is alkyl having l-18 carfor 5 additional hours. Then the precipitate was removed bon atoms. by filtration, washed with ether and pentane and dried 5. The compounds of claim 1 wherein R is alkyl havin vacuo to provide 88.0 g. (85% of the theory) of ing 1-18 carbon atoms and R is aryl having 610 car- N-butyl S-[N-(chlor0carbonyl)-butylamino] isothio- 1O bon atoms. carbamyl chloride, M.P. 133-134 C., in the form of 6. Compounds having the formula 21 microcrystalline powder. 01 01 Analysis.Calcd. for C H Cl N OS: C, 42.09; H, I I 6.32; s, 11.21. Found: c, 42.86; H, 6.35; 5, 11.56. (hahgenated WWW-N:

, 15 R bemg alkyl having l18 carbon atoms. Examples 4 11 7. The compounds of claim 6 wherein R is aryl hav- Using a procedure similar to that utilized in the above ing 610 carbon atoms. examples, a number of other derivatives having the gen- 3, Compounds having the formula eral Formula I have also been prepared. Several of the 01 01 add1t1onal S-[N -(chlorocarbonyl)-am1no] isothiocarbam- 20 I yl chlorides thus prepared are listed in the following (nitrated pheIYD'N; S NC=O table. R being alkyl having 1-18 carbon atoms.

TABLE I Chloride Prepared M.P. Yield, Reactants Having General 0. Percent Formula (I) N-phenyl S-chloro isothiocarbamyl ch10 101-102 77 ride-isopropyl isocyanate. N-phenyl S-ehloro isothiocarbamyl ehlo- 97-99 86 ride-butyl isocyanate. N-phenyl S-ehloro isothiocarbarnyl chlo- 92-93 68 ride-oetyl isocyanate. N-phenyl S-chloro isothiocarbamyl chlo- 74-75 80 ride-phenyl isocyanate. N-phenyl S-ehloro isothiocarbamyl ehlo- 113-114 80-90 ride-p-chlorophenyl isocyanate. N-phenyl S-chloro isothiocarbamyl chlo- {R=phenyl 85-87 -100 ride-p-methoxyphenyl isocyanate. R =p-rnethoxyphenyl..- N-ethyl S-ehloro isothiocarbamyl chlo- {R=ethyl 132-133 78 ride-octyl isocyanate. R=0cty1 N-cyclohexyl S-chloro isothiocarbamyl {R=eyclohexyl 131 60 chloride-isopropyl isocyanate. R=is0propyl The S- [N- chlorocarbonyl -amino] isothiocarbamyl chlorides of this invention are useful as cross linking and chain extending agents in various resin formulations. They are particularly valuable in this regard when used in the preparation of polyurethane and polyamide resins due to the high reactivity of the chlorine atoms with the active hydrogen atoms in the beginning formulations.

They are also valuable intermediates in the preparation of a series of cyclic compounds which are useful agricultural chemicals. It has been found that the compounds (I) react with water to provide derivatives of 1,3,4-oxathiazolidinone having herbicidal and nematocidal properties. For example, N-phenyl S-[N'-(ch1orocarbonyl)-ethylamino] isothiocarbamyl chloride reacts with water at room temperature to provide a nearly quantitative yield of 2 phenylimino 4 ethyl 1,3,4- oxathiazolidin-S-one which is an effective nematocide and herbicide.

What is claimed is:

1. Compounds having the formula 01 Ill (11 9. The compounds of claim 8 wherein R is aryl having 610 carbon atoms.

10. Compounds having the formula with an isocyanate of the Formula RNCO in the presence of an inert diluent, R and R being independent ly selected from the class consisting of alkyl having 1-18 carbon atoms, cycloalkyl having 5-7 carbon atoms, aryl having 6l0 carbon atoms, halogenated phenyl, nitrated phenyl, benzyl and phenyl having a lower alkoxy substituent.

12. The process of claim 11 wherein a reaction temperature range of about 0 C. to about C. is utilized.

No references cited.

LORRAINE A. WEINBERGER, Primary Examiner.

R. JACKSON, Assistant Examiner, 

1. COMPOUNDS HAVING THE FORMULA 